CN1319905C - 氧化镁－氧化锆砖的应用 - Google Patents
氧化镁－氧化锆砖的应用 Download PDFInfo
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- CN1319905C CN1319905C CNB038085054A CN03808505A CN1319905C CN 1319905 C CN1319905 C CN 1319905C CN B038085054 A CNB038085054 A CN B038085054A CN 03808505 A CN03808505 A CN 03808505A CN 1319905 C CN1319905 C CN 1319905C
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000011449 brick Substances 0.000 title claims abstract description 21
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title abstract description 19
- 239000000395 magnesium oxide Substances 0.000 title abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- 230000001172 regenerating effect Effects 0.000 abstract 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 4
- ANOYEYQQFRGUAC-UHFFFAOYSA-N magnesium;oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Zr+4] ANOYEYQQFRGUAC-UHFFFAOYSA-N 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 229910052839 forsterite Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- AGIMJDFJHWOHBM-UHFFFAOYSA-N magnesium oxygen(2-) silicic acid Chemical compound [O-2].[Mg+2].O[Si](O)(O)O AGIMJDFJHWOHBM-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000019739 Dicalciumphosphate Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 1
- 229940038472 dicalcium phosphate Drugs 0.000 description 1
- 229910000390 dicalcium phosphate Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
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- C03B5/235—Heating the glass
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Abstract
本发明涉及一种氧化镁-氧化锆砖在玻璃熔融槽再生室中的应用，该熔融槽至少是部分地在还原气氛下操作。
Description
耐火材料和产品大体上可分为基本产品和非基本产品。
基本类(烧制的)产品包括氧化镁-氧化锆产品(下面将被称作MZA)和以氧化镁-锆石为基础的产品(下面将被称作MZ)。
MZA产品通常是以烧结和/或熔融的氧化镁和二氧化锆(ZrO2)为基础制成的。从矿物学上看，它们包括方镁石(MgO)和稳定的或不稳定的二氧化锆，同时，它们还常常包括，有时是少量的锆酸钙，以及少量的硅酸盐相。
如果二氧化锆是部分或完全稳定的，通过扩散方法可产生直接键合的哦MgO-ZrO2。通过这种方法可改善其机械热特性。
MZA砖具有很高的散裂抵抗力和很高的折射能力。因此，它们主要用于煅烧石灰、白云石、菱镁石，或水泥的旋转管式窑或竖式窑。
典型的一批MZ产品包括烧结的和/或熔融的氧化镁和硅酸锆(ZrO2 xSiO2)。硅酸锆与氧化镁反应生成镁橄榄石和稳定的二氧化锆。通常并不是所有的氧化镁组份都转化成镁橄榄石。因此，矿物学上的方镁石组份仍留在砖中。由于它们良好的耐化学性，特别是耐碱、碱盐和/或SO2/SO3的特性，MZ制品可用于玻璃熔融炉的再生室。
这种MZA/MZ制品的相关技术和典型配方，可见于Gerald Routschka：(ISBN 3-8027-3146-8)的“Taschenbuch feuerfeste Werkstoffe”[防火材料手册]。
本发明涉及本身是已知的产品氧化镁-氧化锆，但也涉及氧化镁-氧化锆产品在玻璃熔融炉再生室中的应用，上述熔融炉至少是暂时地或定期地在一种还原的气氛下操作。
正如前言和Routschka所引用的文献中所述，到目前为止，氧化镁-硅酸锆产品一直都用在玻璃熔融槽的包封中，特别是用在这种包封材料的碱金属硫酸盐的冷凝区。该区的温度为800-1100℃。
为了减少废气中NOx的含量，有人建议玻璃熔融槽应在还原气氛下操作。在这种情况下，废气中NOx的含量可以减少2/3-5/6。
其缺点是，在再生室中的废气一侧发生“束”(”skeins”)的还原，
这会对氧化镁-硅酸锆砖的使用寿命产生不利的影响。材料中至少有部分的镁橄榄石(Mg2SiO4)分解成钠/镁硅酸盐。含CaO的硅酸盐相也会转化。结果，包封材料不再具有所需的稳定性。
令人惊奇的是，现在人们已经确定，如果不使用已知建议用于玻璃槽再生室的MZ产品，而使用以氧化镁-氧化锆(MZA)为基础的产品，就可避免这类问题。
人们对其具有决定性意义的优点表示怀疑的地方在于：这些产品的硅酸盐比例要比MZ产品低得多，因此不会发生上述显微结构的破坏，或发生破坏的程度很小。
ZrO2对碱冷凝区的腐蚀物质具有极好的耐腐蚀性，即使玻璃熔融罐是在还原气氛下操作，而且还原气氛相应地达到再生室。即使玻璃熔融槽只是暂时在还原气氛下操作，情况也是如此。
对要求保护的应用而言，砖(包封砖)的导热系数(MLF)是一个重要的参数，同时，比热容量(C)或相关体积热容量(比热容量c和表观密度R的产品)也是重要的。此外，导热系数与比热容量或体积相关热容量的比例也是值得关注的。
使用所述的MZA产品可以使各种参数得到理想的数值，即：
-高的导热系数可以确保热量理想地快速通过砖，
-比氧化锆砖的比热容量高大约50％的比热容量，例如，可以储存更多的热量。
-理想的/更快的温度平衡使得有可能得到更高的热扩散系数值(超过1m2/秒)。
与C2S键合的氧化镁砖相比，MZA制品也具有显著的优点。C2S产品的硅酸二钙相中的方镁石和CaO会被废气中的SO3分别转化成硫酸盐或硫化物。这又会使砖的显微结构受到破坏。
对所列的应用而言，SiO2的含量(硅酸盐相)越低，砖的特性就越理想。按照一个实施方案，SiO2的含量要低于1.0重量％，按照另一个实施方案，其含量要低于0.5重量％(相对于总批量和/或总的模制部件)。
按照一个实施方案，CaO的含量(例如，CaO可以锆酸钙的形式提供)低于2重量％。
MZA制品的矿物学组成可在已知范围内变动(Routschka，op.Cit.)。
该产品包括5-35重量％ZrO2、65-95重量％MgO和其它组份最多为5重量％。按照另一个实施方案，产品中包括最多2％的其它组份。
按DIN EN 993-第1章测定的开口孔隙率为11-15体积％，或按照一个实施方案为12-14体积％之间。
在1700℃以上温度下烧制之后，表观密度可以达到3.20-3.60g/cm3，或按照一个实施方案可以达到3.25-3.40g/cm3。在这种情况下，表观密度是按DIN EN 993-第1章进行测定。
按DIN EN 993-第5章关于烧制制品的条款进行测定，冷耐压强度为50-150N/mm2，或按照一个实施方案为70-85N/mm2。
导热系数(按Ber.Dtsch.Keram.Ges.[德国陶瓷协会报告]34(1957)，183-189中的其它物品中间的“分类”进行测定)在3-4W/Km(1000℃)的范围内。
一批材料的粒度大小原则上不受限制。可通过二氧化锆矿引入二氧化锆，作为商业生产的二氧化锆(不稳定的、部分稳定的或完全稳定的)的比例在＜0.5mm的范围内，例如，可分成(大约)一半，按照一个实施方案为＜0.1和0.1-0.5mm之间。
按照一个实施方案，烧结氧化镁或熔融氧化镁组份使用的粒度范围达6mm。在这种情况下，＞1mm的组份可能构成2/3氧化镁总加料量的一半。下面将详述两种配方/批次的内容，包括烧制之后所达到的特性特点。
用这种方法制成的砖，成功地在一个工程实验中进行了试验，改善了(玻璃熔融槽)包封操作中所发生的状况。上述砖特别在还原气氛下进行了试验，其本身表明优于传统的氧化镁-硅酸锆砖。
| 样品1 | 样品2 | |
| 氧化镁(MgO)＜1mm | 30％ | 20％ |
| 氧化镁(MgO)＜1-6mm | 50％ | 50％ |
| ZrO2 0.1-0.5mm | 0 | 15 |
| ZrO2＜0.1mm | 20 | 15 |
| 格林表观密度(g/cm3) | 3.32 | 3.46 |
| 烧制(℃) | 1750 | 1750 |
| 烧制后的表观密度(g/cm3) | 3.35 | 3.50 |
| 开口孔隙率(％) | 12.5 | 14 |
| 冷耐压强度(N/mm2) | 55 | 80 |
Claims (6)
1.一种氧化镁-氧化锆砖在玻璃熔融炉再生室中的应用，该熔融炉至少是部分地在还原气氛下操作，上述氧化镁-氧化锆砖中，包括5-35重量％ZrO2、65-95重量％MgO和最多5重量％的其它组份，其中SiO2的含量＜1.0重量％。
2.权利要求1的应用，其中的砖的CaO含量＜2.0重量％。
3.权利要求1的应用，其中的砖包括最多2％的其它组份。
4.权利要求1的应用，其中砖的开口孔隙率为11-15体积％。
5.权利要求1的应用，其中烧制后的砖的表观密度为3.20-3.60g/cm3。
6.权利要求1的应用，其中烧制后的砖的冷耐压强度为50-150N/mm2。
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| Application Number | Priority Date | Filing Date | Title |
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| DE10216879.2 | 2002-04-17 | ||
| DE10216879A DE10216879B4 (de) | 2002-04-17 | 2002-04-17 | Verwendung eines Magnesiazirkoniasteins |
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| US (1) | US7144832B2 (zh) |
| EP (1) | EP1494979B1 (zh) |
| JP (1) | JP2005529302A (zh) |
| KR (1) | KR100769090B1 (zh) |
| CN (1) | CN1319905C (zh) |
| AT (1) | ATE301108T1 (zh) |
| AU (1) | AU2003214097A1 (zh) |
| BR (1) | BR0309310A (zh) |
| DE (2) | DE10216879B4 (zh) |
| ES (1) | ES2244926T3 (zh) |
| MX (1) | MXPA04010110A (zh) |
| PL (1) | PL205180B1 (zh) |
| RU (1) | RU2291133C2 (zh) |
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| US20070213199A1 (en) * | 2006-03-08 | 2007-09-13 | Harbison-Walker Refractories Company | Refractory composition |
| US20070213198A1 (en) * | 2006-03-08 | 2007-09-13 | Harbison-Walker Refractories Company | Refractory composition |
| EP2190792A1 (en) * | 2007-09-03 | 2010-06-02 | Vitro Global, S.A. | Method for melting glass |
| US20090272150A1 (en) * | 2007-11-02 | 2009-11-05 | Lawrence Henry Kotacska | Corrosion-resistant cradle and castable materials for glass production |
| FR2977661B1 (fr) * | 2011-07-07 | 2015-05-08 | Saint Gobain Ct Recherches | Installation thermique a regenerateur et son procede de fabrication |
| CN107266085B (zh) * | 2017-06-09 | 2020-04-17 | 西安建筑科技大学 | 一种锆酸铁钡蓄热材料、制备方法及其应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4451516A (en) * | 1980-09-03 | 1984-05-29 | Ngk Insulators, Ltd. | Low thermal expansion ceramic article |
| BR9103769A (pt) * | 1991-08-30 | 1993-03-30 | Magnesita S A | Composicoes refratarias |
| US6509287B2 (en) * | 2000-06-20 | 2003-01-21 | Societe Europeenne Des Produits Refractaires | Fused cast AZS products of reduced cost |
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|---|---|---|---|---|
| AT225364B (de) * | 1960-07-14 | 1963-01-10 | Oesterr Amerikan Magnesit | Zustellung von Regeneratoren von Industrieöfen |
| US3192059A (en) * | 1963-06-28 | 1965-06-29 | Harbison Walker Refractories | Volume stable refractory and method of making same |
| US3416938A (en) * | 1967-09-05 | 1968-12-17 | Corhart Refractories Co | Mgo-zr-o2 fused cast refractory |
| US3528830A (en) * | 1968-03-05 | 1970-09-15 | Dresser Ind | Refractory composition |
| US4452516A (en) * | 1981-01-23 | 1984-06-05 | Salia Munoz Miguel | Optical grid |
| US4847222A (en) * | 1987-05-04 | 1989-07-11 | Dresser Industries, Inc. | Basic refractory shapes |
| DE3739900A1 (de) * | 1987-11-25 | 1989-06-08 | Didier Werke Ag | Geformte oder ungeformte feuerfestzusammensetzungen auf magnesitbasis und ihre verwendung zum ausmauern von oefen |
| DE4301823C1 (de) * | 1993-01-23 | 1994-05-05 | Veitsch Radex Ag | Feuerfester Stein |
| DE4337916A1 (de) * | 1993-11-06 | 1995-05-11 | Aken Magnesitwerk Gmbh | Geformte und ungeformte Feuerfestzusammensetzungen auf Magnesiabasis |
| JPH11310469A (ja) * | 1998-04-27 | 1999-11-09 | Toshiba Ceramics Co Ltd | ガラス窯蓄熱室用耐火物 |
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- 2003-03-06 KR KR1020047016280A patent/KR100769090B1/ko not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4451516A (en) * | 1980-09-03 | 1984-05-29 | Ngk Insulators, Ltd. | Low thermal expansion ceramic article |
| BR9103769A (pt) * | 1991-08-30 | 1993-03-30 | Magnesita S A | Composicoes refratarias |
| US6509287B2 (en) * | 2000-06-20 | 2003-01-21 | Societe Europeenne Des Produits Refractaires | Fused cast AZS products of reduced cost |
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| Publication number | Publication date |
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| US7144832B2 (en) | 2006-12-05 |
| ES2244926T3 (es) | 2005-12-16 |
| RU2004133664A (ru) | 2006-02-27 |
| JP2005529302A (ja) | 2005-09-29 |
| BR0309310A (pt) | 2005-02-15 |
| RU2291133C2 (ru) | 2007-01-10 |
| DE10216879B4 (de) | 2004-05-06 |
| DE10216879A1 (de) | 2003-11-13 |
| AU2003214097A1 (en) | 2003-10-27 |
| CN1646447A (zh) | 2005-07-27 |
| ZA200408435B (en) | 2006-07-26 |
| US20050164866A1 (en) | 2005-07-28 |
| ATE301108T1 (de) | 2005-08-15 |
| PL371794A1 (en) | 2005-06-27 |
| KR100769090B1 (ko) | 2007-10-23 |
| EP1494979B1 (de) | 2005-08-03 |
| DE50300919D1 (de) | 2005-09-08 |
| MXPA04010110A (es) | 2004-12-13 |
| KR20040111505A (ko) | 2004-12-31 |
| EP1494979A1 (de) | 2005-01-12 |
| PL205180B1 (pl) | 2010-03-31 |
| WO2003087011A1 (de) | 2003-10-23 |
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